Reactive leuco compounds and compositions comprising the same

ABSTRACT

A leuco composition comprises at least one reactive leuco compound, which reactive leuco compound comprises a leuco moiety and at least one reactive moiety covalently bound to the leuco moiety. A laundry care composition comprises a laundry care ingredient and a leuco composition. A method of treating a textile comprises the steps of (i) treating a textile with an aqueous solution containing a leuco composition, (ii) optionally, rinsing the textile, and (iii) drying the textile.

TECHNICAL FIELD

This application describes reactive leuco compounds, laundry carecompositions containing such reactive leuco compounds, and the use ofsuch compounds and compositions in the laundering of textile articles.These types of compounds are provided in a stable, substantiallycolorless state and then may be transformed to an intense colored stateupon exposure to certain physical or chemical changes such as, forexample, exposure to oxygen, ion addition, exposure to light, and thelike. The laundry care compositions containing the leuco compounds aredesigned to enhance the apparent or visually perceived whiteness of, orto impart a desired hue to, textile articles washed or otherwise treatedwith the laundry care composition.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. As such, to visually enhance these textilesubstrates and counteract the fading and yellowing the use of polymericcolorants for coloring consumer products has become well known in theprior art. For example, it is well known to use whitening agents, eitheroptical brighteners or bluing agents, in textile applications. However,traditional whitening agents tend to lose efficacy upon storage due todeleterious interactions with other formulation components (such as, forexample, perfumes). Further, such whitening agents can suffer from poordeposition on textile substrates. As such, formulators tend to increasethe level of whitening agent used to counteract any efficacy lost uponstorage and/or to increase the amount of whitening agent available todeposit on the textile substrate.

Leuco dyes are also known in the prior art to exhibit a change from acolorless or slightly colored state to a colored state upon exposure tospecific chemical or physical triggers. The change in coloration thatoccurs is typically visually perceptible to the human eye. All existingcompounds have some absorbance in the visible light region (400-750 nm),and thus more or less have some color. In this invention, a dye isconsidered as a “leuco dye” if it did not render a significant color atits application concentration and conditions, but renders a significantcolor in its triggered form. The color change upon triggering stems fromthe change of the molar attenuation coefficient (also known as molarextinction coefficient, molar absorption coefficient, and/or molarabsorptivity in some literatures) of the leuco dye molecule in the400-750 nm range, preferably in the 500-650 nm range, and mostpreferably in the 530-620 nm range. The increase of the molarattenuation coefficient of a leuco dye before and after the triggeringshould be greater than 50%, more preferably greater than 200%, and mostpreferably greater than 500%.

As such, there remains a need for an effective whitening agent thateffectively deposits on textile substrates.

It has now surprisingly been found that the presently claimed reactiveleuco compounds not only provide the desired consumer whiteness benefit,but laundry care compositions (e.g., detergents) containing thesecompounds deliver increasing whiteness. Furthermore, it has surprisinglybeen found that hydrolyzed derivatives of such reactive leuco compoundscan be used to impart the desired consumer whiteness benefit with theprospect of reducing the risk of irritation and/or sensitization of therespiratory tract and/or skin typically associated with reactivecompounds.

SUMMARY OF THE INVENTION

In a first embodiment, the invention provides a leuco compositioncomprising at least one reactive leuco compound, the reactive leucocompound comprising a leuco moiety and at least one reactive moietycovalently bound to the leuco moiety. The reactive moiety preferably issufficiently electrophilic to react with a nucleophilic moiety selectedfrom the group consisting of amine groups, hydroxy groups, andsulfhydryl groups. The ratio of the amount of the reactive leucocompound present in the composition to the amount of a colored form ofthe reactive leuco compound present in the leuco composition is about 1(or more):9.

In a second embodiment, the invention provides a laundry carecomposition comprising a laundry care ingredient and a leuco compositionas described herein. In one aspect, the invention provides a laundrycare composition comprising: (i) from 2 to 70 wt. % of a surfactant; and(ii) from 0.0001 to 20.0 wt. % of a leuco composition as describedherein.

In a third embodiment, the invention provides a method of treating atextile comprises the steps of (i) treating a textile with an aqueoussolution containing a leuco composition as described herein, (ii)optionally, rinsing the textile, and (iii) drying the textile. In oneaspect, the invention provides a method of treating a textile comprisingthe steps of: (i) treating a textile with an aqueous solution containinga leuco composition as described herein, the aqueous solution comprisingfrom 10 ppb to 5000 ppm of at least one reactive leuco compound and from0.0 g/L to 3 g/L of a surfactant; (ii) optionally rinsing; and (iii)drying the textile.

DETAILED DESCRIPTION

Definitions

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the interchangeable terms “alkyleneoxy” and“oxyalkylene,” and the interchangeable terms “polyalkyleneoxy” and“polyoxyalkylene,” generally refer to molecular structures containingone or more than one, respectively, of the following repeating units:—C₂H₄O—, —C₃H₆O—, —C₄H₈O—, and any combinations thereof. Non-limitingstructures corresponding to these groups include —CH₂CH₂O—,—CH₂CH₂CH₂O—, —CH₂CH₂CH₂CH₂O—, —CH₂CH(CH₃)O—, and —CH₂CH(CH₂CH₃)O—, forexample. Furthermore, the polyoxyalkylene constituent may be selectedfrom the group consisting of one or more monomers selected from a C₂₋₂₀alkyleneoxy group, a glycidyl group, or mixtures thereof.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the terms “alkyl” and “alkyl capped” are intended tomean any univalent group formed by removing a hydrogen atom from asubstituted or unsubstituted hydrocarbon. Non-limiting examples includehydrocarbyl moieties which are branched or unbranched, substituted orunsubstituted including C₁-C₁₈ alkyl groups, and in one aspect, C₁-C₆alkyl groups.

As used herein, unless otherwise specified, the term “aryl” is intendedto include C₃-C₁₂ aryl groups. The term “aryl” refers to bothcarbocyclic and heterocyclic aryl groups.

As used herein, the term “alkaryl” refers to any alkyl-substituted arylsubstituents and aryl-substituted alkyl substituents. More specifically,the term is intended to refer to C₇₋₁₆ alkyl-substituted arylsubstituents and C₇₋₁₆ aryl substituted alkyl substituents which may ormay not comprise additional substituents.

As used herein, the term “detergent composition” is a sub-set of laundrycare composition and includes cleaning compositions including but notlimited to products for laundering fabrics. Such compositions may bepre-treatment composition for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and “stain-stick” or pre-treat types.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions, including but not limited to products for launderingfabrics, fabric softening compositions, fabric enhancing compositions,fabric freshening compositions, and other products for the care andmaintenance of fabrics, and combinations thereof. Such compositions maybe pre-treatment compositions for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and/or “stain-stick” or pre-treat compositions orsubstrate-laden products such as dryer added sheets.

As used herein, the term “leuco” (as used in reference to, for example,a compound, moiety, radical, dye, monomer, fragment, or polymer) refersto an entity (e.g., organic compound or portion thereof) that, uponexposure to specific chemical or physical triggers, undergoes one ormore chemical and/or physical changes that results in a shift from afirst color state (e.g., uncolored or substantially colorless) to asecond more highly colored state. Suitable chemical or physical triggersinclude, but are not limited to, oxidation, pH change, temperaturechange, and changes in electromagnetic radiation (e.g., light) exposure.Suitable chemical or physical changes that occur in the leuco entityinclude, but are not limited to, oxidation and non-oxidative changes,such as intramolecular cyclization. Thus, in one aspect, a suitableleuco entity can be a reversibly reduced form of a chromophore. In oneaspect, the leuco moiety preferably comprises at least a first and asecond π-system capable of being converted into a third combinedconjugated π-system incorporating said first and second π-systems uponexposure to one or more of the chemical and/or physical triggersdescribed above.

As used herein, the terms “leuco composition” or “leuco colorantcomposition” refers to a composition comprising at least two leucocompounds having independently selected structures as described infurther detail herein.

As used herein “average molecular weight” of the leuco colorant isreported as a weight average molecular weight, as determined by itsmolecular weight distribution: as a consequence of their manufacturingprocess, the leuco colorants disclosed herein may contain a distributionof repeating units in their polymeric moiety.

As used herein, the terms “maximum extinction coefficient” and “maximummolar extinction coefficient” are intended to describe the molarextinction coefficient at the wavelength of maximum absorption (alsoreferred to herein as the maximum wavelength), in the range of 400nanometers to 750 nanometers.

As used herein, the term “first color” is used to refer to the color ofthe laundry care composition before triggering, and is intended toinclude any color, including colorless and substantially colorless.

As used herein, the term “second color” is used to refer to the color ofthe laundry care composition after triggering, and is intended toinclude any color that is distinguishable, either through visualinspection or the use of analytical techniques such asspectrophotometric analysis, from the first color of the laundry carecomposition.

As used herein, the term “converting agent” refers to any oxidizingagent as known in the art other than molecular oxygen in any of itsknown forms (singlet and triplet states).

As used herein, the term “triggering agent” refers to a reactantsuitable for converting the leuco composition from a colorless orsubstantially colorless state to a colored state.

As used herein, the term “whitening agent” refers to a dye or a leucocolorant that may form a dye once triggered that when on white cottonprovides a hue to the cloth with a relative hue angle of 210 to 345, oreven a relative hue angle of 240 to 320, or even a relative hue angle of250 to 300 (e.g., 250 to 290).

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include/s” and “including” are meant to benon-limiting.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

In one aspect, the molar extinction coefficient of said second coloredstate at the maximum absorbance in the wavelength in the range 200 to1,000 nm (more preferably 400 to 750 nm) is preferably at least fivetimes, more preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the molar extinction coefficient of saidfirst color state at the wavelength of the maximum absorbance of thesecond colored state. Preferably, the molar extinction coefficient ofsaid second colored state at the maximum absorbance in the wavelength inthe range 200 to 1,000 nm (more preferably 400 to 750 nm) is at leastfive times, preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the maximum molar extinction coefficient ofsaid first color state in the corresponding wavelength range. Anordinarily skilled artisan will realize that these ratios may be muchhigher. For example, the first color state may have a maximum molarextinction coefficient in the wavelength range from 400 to 750 nm of aslittle as 10 M⁻¹cm⁻¹, and the second colored state may have a maximummolar extinction coefficient in the wavelength range from 400 to 750 nmof as much as 80,000 M⁻¹cm⁻¹ or more, in which case the ratio of theextinction coefficients would be 8,000:1 or more.

In one aspect, the maximum molar extinction coefficient of said firstcolor state at a wavelength in the range 400 to 750 nm is less than 1000M⁻¹cm⁻¹, and the maximum molar extinction coefficient of said secondcolored state at a wavelength in the range 400 to 750 nm is more than5,000 M⁻¹cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹cm⁻¹. A skilled artisan will recognize and appreciate that apolymer comprising more than one leuco moiety may have a significantlyhigher maximum molar extinction coefficient in the first color state(e.g., due to the additive effect of a multiplicity of leuco moieties orthe presence of one or more leuco moieties converted to the secondcolored state). Where more than one leuco moiety is attached to amolecule, the maximum molar extinction coefficient of said second colorstate may be more than n×□ where n is the number of leuco moieties plusoxidized leuco moieties present on the molecule, and □ is selected from5,000 M⁻¹cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹cm⁻¹. Thus for a molecule that has two leuco moieties, themaximum molar extinction coefficient of said second color state may bemore than 10,000 M⁻¹cm⁻¹, preferably more than 20,000, 50,000, 100,000or even 200,000 M⁻¹cm⁻¹. While n could theoretically be any integer, oneskilled in the art appreciates that n will typically be from 1 to 100,more preferably 1 to 50, 1 to 25, 1 to 10 or even 1 to 5.

The present invention relates to a class of leuco colorants that may beuseful for use in laundry care compositions, such as liquid laundrydetergent, to provide a blue hue to whiten textile substrates. Leucocolorants are compounds that are essentially colorless or only lightlycolored but are capable of developing an intense color upon activation.One advantage of using leuco compounds in laundry care compositions isthat such compounds, being colorless until activated, allow the laundrycare composition to exhibit its own color. The leuco colorant generallydoes not alter the primary color of the laundry care composition. Thus,manufacturers of such compositions can formulate a color that is mostattractive to consumers without concern for added ingredients, such asbluing agents, affecting the final color value of the composition.

As noted above, in a first embodiment, the invention a leuco compositioncomprising at least one reactive leuco compound, the reactive leucocompound comprising a leuco moiety and at least one reactive moietycovalently bound to the leuco moiety.

The reactive leuco compound can comprise any suitable leuco moiety asdefined above. In one aspect, the leuco moiety preferably is selectedfrom the group consisting diarylmethane leuco moieties, triarylmethaneleuco moieties, oxazine moieties, thiazine moieties, hydroquinonemoieties, and arylaminophenol moieties and mixtures thereof.

Suitable diarylmethane leuco compounds for use herein include, but arenot limited to, diarylmethylene derivatives capable of forming a secondcolored state as described herein. Suitable examples include, but arenot limited to, Michler's methane, a diarylmethylene substituted with an—OH group (e.g., Michler's hydrol) and ethers and esters thereof, adiarylmethylene substituted with a photocleavable moiety, such as a —CNgroup (bis(para-N,N-dimethyl)phenyl)acetonitrile), and similar suchcompounds.

In a more particular preferred aspect, the leuco moiety is a univalentor polyvalent moiety derived by removal of one or more hydrogen atomsfrom a structure of Formula (I), (II), (III), (IV), or (V) below

wherein the ratio of Formula I-V to its oxidized form is at least 1:19,1:9, or 1:3, preferably at least 1:1, more preferably at least 3:1, mostpreferably at least 9:1 or even 19:1.

In the structure of Formula (I), wherein each individual R_(o), R_(m)and R_(p) group on each of rings A, B and C is independently selectedfrom the group consisting of hydrogen, deuterium and R⁵; each R⁵ isindependently selected from the group consisting of halogens, nitro,alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substitutedalkaryl, —(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻,—C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹,—S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,—NR¹C(O)NR²R³, —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂,wherein the index n is an integer from 0 to 4, preferably from 0 to 1,most preferably 0; wherein two R_(o) on different A, B and C rings maycombine to form a fused ring of five or more members; when the fusedring is six or more members, two R_(o) on different A, B and C rings maycombine to form an organic linker optionally containing one or moreheteroatoms; in one embodiment two R_(o) on different A, B and C ringscombine to form a heteroatom bridge selected from —O— and —S— creating asix member fused ring; an R_(o) and R_(m) on the same ring or an R_(m)and R_(p) on the same ring may combine to form a fused aliphatic ring orfused aromatic ring either of which may contain heteroatoms; on at leastone of the three rings A, B or C, preferably at least two, morepreferably at least three, most preferably all four of the R_(o) andR_(m) groups are hydrogen, preferably all four R_(o) and R_(m) groups onat least two of the rings A, B and C are hydrogen; in some embodiments,all R_(o) and R_(m) groups on rings A, B and C are hydrogen; preferablyeach R_(p) is independently selected from hydrogen, —OR¹ and —NR¹R²; nomore than two, preferably no more than one of R_(p) is hydrogen,preferably none are hydrogen; more preferably at least one, preferablytwo, most preferably all three R_(p) are —NR¹R²; in some embodiments,one or even two of the Rings A, B and C may be replaced with anindependently selected C₃-C₉ heteroaryl ring comprising one or twoheteroatoms independently selected from O, S and N, optionallysubstituted with one or more independently selected R⁵ groups; G isindependently selected from the group consisting of hydrogen, deuterium,C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite, nitrile, alkyl amine,imidazole, arylamine, polyalkylene oxide, halides, alkylsulfide, arylsulfide, or phosphine oxide; in one aspect the fraction[(deuterium)/(deuterium+hydrogen)] for G is at least 0.20, preferably atleast 0.40, even more preferably at least 0.50 and most preferably atleast 0.60 or even at least 0.80.

In the structures of Formula (II) and (III), wherein e and f areindependently integers from 0 to 4; each R²⁰ and R²¹ is independentlyselected from the group consisting of halogens, a nitro group, alkylgroups, substituted alkyl groups, —NC(O)OR¹, —NC(O)SR¹, —(CH₂)_(n)—O—R¹,and —(CH₂)_(n)—NR¹R², wherein the index n is an integer from 0 to 4,preferably from 0 to 1, most preferably 0; each R²⁵ is independentlyselected from the group consisting of monosaccharide moiety,disaccharide moiety, oligosaccharide moiety, and polysaccharide moiety,—C(O)R¹, —C(O)OR¹, —C(O)NR¹R²; and each R²² and R²³ is independentlyselected from the group consisting of hydrogen, alkyl groups, andsubstituted alkyl groups.

In the structure of Formula (IV), wherein R³⁰ is positioned ortho orpara to the bridging amine moiety and is selected from the groupconsisting of —OR³⁸ and —NR³⁶R³⁷, each R³⁶ and R³⁷ is independentlyselected from the group consisting of hydrogen, alkyl groups,substituted alkyl groups, aryl groups, substituted aryl groups, acylgroups, R⁴, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; R³⁸ is selected from thegroup consisting of hydrogen, acyl groups, —C(O)OR¹, —C(O)R¹, and—C(O)NR¹R²; g and h are independently integers from 0 to 4; each R³¹ andR³² is independently selected from the group consisting of alkyl groups,substituted alkyl groups, aryl groups, substituted aryl groups, alkaryl,substituted alkaryl, —(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², —C(O)R¹,—C(O)OR¹, —C(O)O⁻, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R²,—S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR²,—NR¹C(O)SR², —NR¹C(O)NR²R³, —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and—P(O)(O⁻)₂, wherein the index n is an integer from 0 to 4, preferablyfrom 0 to 1, most preferably 0; —NR³⁴R³⁵ is positioned ortho or para tothe bridging amine moiety and R³⁴ and R³⁵ are independently selectedfrom the group consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, and R⁴; R³³ isindependently selected from the group consisting of hydrogen, —S(O)₂R¹,—C(O)N(H)R¹; —C(O)OR¹; and —C(O)R¹; when g is 2 to 4, any two adjacentR³¹ groups may combine to form a fused ring of five or more memberswherein no more than two of the atoms in the fused ring may be nitrogenatoms.

In the structure of Formula (V), X⁴⁰ is selected from the groupconsisting of an oxygen atom, a sulfur atom, and NR⁴⁵; R⁴⁵ isindependently selected from the group consisting of hydrogen, deuterium,alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substitutedalkaryl, —S(O)₂OH, —S(O)₂O⁻, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; R⁴⁰ andR⁴¹ are independently selected from the group consisting of—(CH₂)_(n)—O—R¹, —(CH₂)_(n)—NR¹R², wherein the index n is an integerfrom 0 to 4, preferably from 0 to 1, most preferably 0; j and k areindependently integers from 0 to 3; R⁴² and R⁴³ are independentlyselected from the group consisting of alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —S(O)₂R¹, —C(O)NR¹R²,—NC(O)OR¹, —NC(O)SR¹, —C(O)OR¹, —C(O)R¹, —(CH₂)_(n)—O—R¹,—(CH₂)_(n)—NR¹R², wherein the index n is an integer from 0 to 4,preferably from 0 to 1, most preferably 0; R⁴⁴ is —C(O)R¹, —C(O)NR¹R²,and —C(O)OR¹.

In the structures of Formula (1)-(V), wherein any charge present in anyof the preceding groups is balanced with a suitable independentlyselected internal or external counterion. Suitable independentlyselected external counterions may be cationic or anionic. Examples ofsuitable cations include but are not limited to one or more metalspreferably selected from Group I and Group II, the most preferred ofthese being Na, K, Mg, and Ca, or an organic cation such as iminium,ammonium, and phosphonium. Examples of suitable anions include but arenot limited to: fluoride, chloride, bromide, iodide, perchlorate,hydrogen sulfate, sulfate, aminosulfate, nitrate, dihydrogen phosphate,hydrogen phosphate, phosphate, bicarbonate, carbonate, methosulfate,ethosulfate, cyanate, thiocyanate, tetrachlorozincate, borate,tetrafluoroborate, acetate, chloroacetate, cyanoacetate, hydroxyacetate,aminoacetate, methylaminoacetate, di- and tri-chloroacetate,2-chloro-propionate, 2-hydroxypropionate, glycolate, thioglycolate,thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate,acrylate, oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzenesulfonate, toluenesulfonate, biphenyl-sulfonate andchlorotoluenesulfonate. Those of ordinary skill in the art are wellaware of different counterions which can be used in place of thoselisted above.

In the structures of Formula (I)-(V), R¹, R², R³, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,and R⁴; wherein R⁴ is a organic group composed of one or more organicmonomers with said monomer molecular weights ranging from 28 to 500,preferably 43 to 350, even more preferably 43 to 250, wherein theorganic group may be substituted with one or more additional leucocolorant moieties conforming to the structure of Formula I-V. In oneaspect, R⁴ is selected from the group consisting of alkyleneoxy(polyether), oxoalkyleneoxy (polyesters), oxoalkyleneamine (polyamides),epichlorohydrin, quaternized epichlorohydrin, alkyleneamine,hydroxyalkylene, acyloxyalkylene, carboxyalkylene, carboalkoxyalkylene,and sugar. Where any leuco moiety comprising an R⁴ group with three ormore contiguous monomers, that leuco moiety is defined herein as a“polymeric leuco moiety”. One skilled in the art knows that theproperties of a compound with regard to any of a number ofcharacteristic attributes such as solubility, partitioning, deposition,removal, staining, etc., are related to the placement, identity andnumber of such contiguous monomers incorporated therein. The skilledartisan can therefore adjust the placement, identity and number of suchcontiguous monomers to alter any particular attribute in a more or lesspredictable fashion.

As noted above, the reactive leuco compound(s) present in the leucocomposition comprise at least one reactive moiety covalently bound tothe leuco moiety. The reactive moiety can be any suitable electrophilicmoiety. Suitable electrophilic moieties are those that are sufficientlyelectrophilic to react with an organic nucleophilic moiety having aresonance structure (contributing structure) in which a lone pair ofelectrons or a negative charge resides on a carbon, nitrogen, oxygen,sulfur, or phosphorus atom within the moiety. Upon reacting, thereactive moiety creates a covalent bond between the leuco moiety and thecompound containing the organic nucleophilic moiety. Preferably, thereactive moiety is sufficiently electrophilic to react with anucleophilic moiety selected from the group consisting of a hydroxygroup, a sulfhydryl group, a cyano group, alkoxy groups, amine groups(primary, secondary, or tertiary amines), carbanions, carboxyl groups,thiocarboxylate groups, thiolate groups, and thiocyanate groups. Inanother preferred embodiment, the reactive moiety is sufficientlyelectrophilic to react with a nucleophilic moiety selected from thegroup consisting of a hydroxy group, a sulfhydryl group, and aminegroups.

Suitable reactive moieties include, but are not limited to, thosemoieties which react with an amine to form a carbamate, a urea, anamide, a sulfonamide, or a higher order amine (such as secondary aminefrom a primary amine, or a tertiary amine from a secondary amine, viaalkylation). Suitable reactive moieties also include, but are notlimited to, those moieties which react with an alcohol to formcarbonates, carbamates, carboxylic acid esters, sulfonic acid esters, orethers. Suitable reactive moieties also include, but are not limited to,those moieties which react with a sulfhydryl (thiol) to formthiocarbonates, thiocarbamates, and the like. Suitable reactive moietiesinclude, but are not limited to, those illustrated below:

In the structures above, the index n is 0 or 1. When n is 1, reaction ofthe above groups with an amine forms a carbamate, and reaction with analcohol forms a carbonate. When n is 0, the product of reaction with anamine is a carboxylic acid amide, and the product of reaction with analcohol is a carboxylic acid ester. Similar groups suitable for theformation of sulfonic acid esters and amides are well known to thoseskilled in the art. In like manner, alkyl halides and alkyl tosylatesare representative of reactive groups that may react with an amine toform a higher order amine, or with an alcohol to form an ether.

In addition to the more traditional groups that may be used as reactivemoieties, any of the many specialized electrophilic moieties that havebeen employed as anchoring groups for reactive dyes may be profitablyemployed. Reactive dyes consist of a dye chromophore covalently bound toa reactive moiety. These reactive moieties react with nucleophilicmoieties (e.g., primary and secondary amines) to form a covalent bound,preferably by a substitution or addition reaction.

Reactive moieties of this sort are preferably selected from heterocyclicreactive moieties and a sulfooxyethylsulfonyl reactive group(—SO₂CH₂CH₂OSO₃Na). The heterocyclic reactive moieties are preferablynitrogen contains aromatic rings bound to a halogen or an ammonium m,which react with nucleophilic moieties (e.g., primary amines and secondamines) of another compound to form a covalent bond. These heterocyclicreactive moieties preferably contain a halogen, such as chlorine orfluorine. In a preferred embodiment, the reactive moiety preferably isselected from the group consisting of sulfooxyethylsulfonyl moieties,vinylsulfonyl moieties, halotriazinyl moieties, quaternaryammoniumtriazinyl moieties, halopyrimidinyl moieties, halopyridazinylmoieties, haloquinoxalinyl moieties, halophthalazinyl moieties,bromoacrlyamidyl moieties, and benzothiazolyl moieties. More preferredheterocylic reactive moieties are dichlorotriazinyl,difluorochloropyrimi-dine, monofluorotrazinyl, monofluorochlorotrazinyl,dichloroquinoxaline, difluorotriazine, monochlorotriazinyl, andtrichloropyrimidine.

Especially preferred heterocylic reactive moieties are:

wherein R¹ is selected from H or alkyl, preferably H; X is selected fromF or Cl; when X═Cl, Z¹ is selected from —Cl, —NR²R³, —OR², —SO₃Na; whenX═F, Z¹ is selected from —NR²R³ wherein R² and R³ are independentlyselected from H, alkyl and aryl groups. Aryl groups are preferablyphenyl and are preferably substituted by —SO₃Na or —SO₂CH₂CH₂OSO₃Na.Alkyl groups are preferably methyl or ethyl. The phenyl groups may befurther substituted with suitable uncharged organic groups, preferablywith a molecular weight lower than 200. Preferred groups include —CH₃,—C₂H₅, and —OCH₃. The alkyl groups may be further substituted withsuitable uncharged organic groups, preferably with a molecular weightlower than 200. Preferred groups include —CH₃, —C₂H₅, —OH, —OCH₃,—OC₂H₄OH. Most preferred heterocylic reactive moieties are selectedfrom:

wherein m=1 or 2, preferably 1.

In another aspect, the reactive moiety is selected from the groupconsisting of:

wherein R₃ is —OSO₃X, —OSO₃ ⁻, or —Cl. R₄ and R₅ are independentlyselected from —Cl and —Br; R₁ and R₂ are independently selected from—Cl, —F, and the radical selected from:

where R₁₀ is selected from H, —CO₂X where X is hydrogen or a cation ofan alkali or alkaline earth metal or an ammonium.

In the reactive leuco compound, the reactive moiety can be directlybound to the leuco moiety or the two can be connected by any suitablelinking moiety. Suitable linking moieties include, but are not limitedto, oxygen, an amine, and alkanediyl moieties. Suitable alkanediylmoieties include, but are not limited to, branched and unbranched C₁-C₈alkanediyl moieties, more preferably branched and unbranched C₁-C₄alkanediyl groups (e.g., an ethane-1,2-diyl moiety).

Suitable reactive leuco compounds include, but are not limited to,derivatives of cyanuric chloride (2,4,6-trichloro-1,3,5-triazine[108-77-0]), a molecule of wide synthetic potential because the threechlorine atoms on the triazine ring differ in their reactivities. Thefirst chlorine atom exchanges with nucleophiles in water at 0-5° C., thesecond at 35-40° C., and the third at 80-85° C. A wide variety oftriazinyl based leuco compounds can thus be prepared by carefulselection of the reaction conditions. Condensation of cyanuric chloridewith a leuco compound (“leuco” in the structures that following)containing an amino group (the amino group may be linked directly to theleuco compound or via a bridging moiety) yields the highly reactivedichlorotriazinyl compounds 1. These very reactive leuco compounds aresensitive to hydrolysis, and a suitable buffer can be added to increaseits stability.

When two of the chlorine atoms are substituted, for example with aminoor alkoxyl groups, monochlorotriazinyl leuco compounds 2 are obtained(where X═—NR₂, —NHR, —OR, or —SR). These are considerably less reactive,and hence react with cellulose or other molecules comprisingnucleophilic moieties (such as —OH, —SH and amines) only at relativelyhigh temperature (for example, 80° C.).

The reactivity of monochlorotriazinyl leuco compounds can be increasedby replacing chlorine with fluorine (3), which allows the process to becarried out at lower temperatures, such as 40° C.

Reaction of monochlorotriazinyl leuco compounds with tertiary aminesalso yields highly reactive leuco compounds 4. One advantage conferredby the ammonium groups in these compounds is increased water solubility.

The reactivity of compounds of this type is strongly influenced by thechoice of tertiary amine. Nicotinic acid is preferred because it acts asa good leaving group and introduces comparatively little odor tocompositions containing the compound. The ammonium residue is also abetter leaving group than, for example, chlorine, and allows theattachment process to be conducted at 40-60° C. In contrast tohalogen-containing triazinyl leuco compounds, these leuco compounds donot require alkali in the application process, so attachment can beconducted under neutral conditions.

In addition to the 1,3,5-triazines, other classes of heterocycles areimportant as reactive moieties. Especially noteworthy are thehalopyrimidine-based leuco compounds 5.

These compounds are less reactive than the triazines because the extracarbon atom reduces the ability of the ring to stabilize a negativecharge. The reactivity of the system can be increased by introducingstrongly electron withdrawing groups, including cyano, fluoro, ormethylsulfonyl groups. The pyrimidine ring can also be activated byinserting a carbonyl group between the leuco moiety and the heterocycle(6).

Other diazine moieties can also be incorporated into reactive leucocompounds, e.g., 7 and 8:

The list of economically attractive reactive heterocyclic intermediatesalso includes dichloroquinoxalines 9 and dichlorophthalazines 10.Reactive moieties in both cases are bound to the leuco moiety via acarbonylamino group, and the reactivities correspond roughly to those ofdichlorotriazinyl-based compounds.

Benzothiazole derivatives with good leaving groups at the 2-position ofthe heterocycle can also be used as reactive moieties. An example ofsuch a reactive leuco compound with chlorine as the leaving group is 11.

The reactive moiety that has had the greatest impact on the market isthe 2-sulfooxyethylsulfonyl group. Treatment with alkali in this casecauses the elimination of sulfuric acid to form a vinylsulfonyl moietythat reacts with desired nucleophiles to provide a bond. Describing thisas an elimination-addition sequence is not meant to rule out thepossibility that the nucleophile attacks the -carbon atom directly,without intervention of a vinyl intermediate. Reactive vinylsulfones arealso prepared from 2-chloroethylsulfonyl derivatives, which lead to thedesired intermediates by elimination of hydrogen chloride:

Numerous derivatives of ethylsulfonyl and vinylsulfonyl groups have alsobeen prepared in recent years, and such derivatives are also believed tobe suitable reactive moieties for the reactive leuco compounds describedherein.

In one aspect, the reactive leuco compound comprises more than onereactive moiety, preferably two or three. In such embodiments, thereactive moieties can be the same or different. One example of areactive leuco compound containing multiple different reactive moietiesis a compound in which cyanuric chloride is bound to an amine with twoaliphatic 2-chloroethylsulfonyl chains (16):

The leuco composition of the invention can contain the colored form ofany reactive leuco compound(s) present in the leuco composition. In apreferred embodiment, the ratio of the amount of the reactive leucocompound present in the leuco composition to the amount of a coloredform of the reactive leuco compound present in the leuco composition isabout 1:9 or more. More preferably, the ratio of the amount of thereactive leuco compound present in the composition to the amount of acolored form of the reactive leuco compound present in the leucocomposition is about 1:4 or more, about 1:3 or more, about 3:7 or more,about 2:3 or more, about 1:1 or more, about 3:2 or more, about 7:3 ormore, about 3:1 or more, about 4:1 or more, or about 9:1 or more.

The leuco compounds described above are believed to be suitable for usein the treatment of textile materials, such as in domestic launderingprocesses. In particular, it is believed that the leuco compounds willdeposit onto the fibers of the textile material due to the nature of theleuco compound. Further, once deposited onto the textile material, theleuco compound can be converted to a colored compound through theapplication of the appropriate chemical or physical triggers that willconvert the leuco compound to its colored form. For example, the leucocompound can be converted to its colored form upon oxidation of theleuco compound to the oxidized compound. By selecting the proper leucomoiety, the leuco compound can be designed to impart a desired hue tothe textile material as the leuco compound is converted to its coloredform. For example, a leuco compound that exhibits a blue hue uponconversion to its colored form can be used to counteract the yellowingof the textile material to normally occurs due to the passage of timeand/or repeated launderings. Thus, in other embodiments, the inventionprovides laundry care compositions comprising the above-described leucocompound and domestic methods for treating a textile material (e.g.,methods for washing an article of laundry or clothing).

Preferably the leuco compound gives a hue to the cloth with a relativehue angle of 210 to 345, or even a relative hue angle of 240 to 320, oreven a relative hue angle of 250 to 300 (e.g., 250 to 290). The relativehue angle can be determined by any suitable method as known in the art.However, preferably it may be determined as described in further detailherein with respect to deposition of the leuco entity on cotton relativeto cotton absent any leuco entity.

In one embodiment, the invention provides a leuco composition comprisinga hydrolyzed reactive leuco compound. The hydrolyzed reactive leucocompound can be any compound obtainable by reaction of a reactive leucocompound described above and water. In a preferred embodiment, theelectrophilic moiety has been hydrolyzed to a moiety selected from thegroup consisting of heteroaromatic moieties having at least one hydroxygroup covalently bound thereto and —SO₂CH₂CH₂OH.

In one embodiment, the invention provides a leuco composition that isproduced by reacting a leuco composition and/or reactive leuco compoundas described above with an organic compound comprising a nucleophilicmoiety. Suitable nucleophilic moieties include, but are not limited to,primary amine groups, secondary amine groups, hydroxy groups, andsulfhydryl groups. The organic compound can be any suitable compoundcomprising a nucleophilic moiety. For example, the organic compound canbe a polymer or any laundry care ingredient described below thatcontains one or more nucleophilic moieties. In certain embodiments, thisleuco composition can be combined with the hydrolyzed leuco compositiondescribed above to yield another leuco composition.

The amount of reactive leuco compound(s), hydrolyzed reactive leucocompound(s), and/or product of a reactive leuco compound with an organiccompound comprising a nucleophilic moiety, all of which will simply bereferred to here and in the paragraph below as reactive leucocompound(s), used in the laundry care compositions of the presentinvention may be any level suitable to achieve the aims of theinvention. In one aspect, the laundry care composition comprisesreactive leuco compound in an amount from about 0.0001 wt % to about 1.0wt %, preferably from 0.0005 wt % to about 0.5 wt %, even morepreferably from about 0.0008 wt % to about 0.2 wt %, most preferablyfrom 0.004 wt % to about 0.1 wt %.

In another aspect, the laundry care composition comprises reactive leucocompound in an amount from 0.0025 to 5.0 milliequivalents/kg, preferablyfrom 0.005 to 2.5 milliequivalents/kg, even more preferably from 0.01 to1.0 milliequivalents/kg, most preferably from 0.05 to 0.50milliequivalents/kg, wherein the units of milliequivalents/kg refer tothe milliequivalents of leuco moiety per kg of the laundry composition.For reactive leuco compound comprising more than one leuco moiety, thenumber of milliequivalents is related to the number of millimoles of thereactive leuco compound by the following equation: (millimoles ofreactive leuco compound)×(no. of milliequivalents of leucomoiety/millimole of reactive leuco compound)=milliequivalents of leucomoiety. In instances where there is only a single leuco moiety perreactive leuco compound, the number of milliequivalents/kg will be equalto the number of millimoles of reactive leuco compound/kg of the laundrycare composition.

As noted above, in a second embodiment, the invention provides a laundrycare composition comprising a laundry care ingredient and a leucocomposition as described herein. The laundry care composition cancomprise any suitable leuco composition or combination of leucocompositions as described herein. The laundry care composition cancomprise any suitable laundry care ingredient. Laundry care ingredientssuitable for use in the invention are described in detail below.

Laundry Care Ingredients

Surfactant System

The products of the present invention may comprise from about 0.00 wt %,more typically from about 0.10 to 80% by weight of a surfactant. In oneaspect, such compositions may comprise from about 5% to 50% by weight ofsurfactant. Surfactants utilized can be of the anionic, nonionic,amphoteric, ampholytic, zwitterionic, or cationic type or can comprisecompatible mixtures of these types. Anionic and nonionic surfactants aretypically employed if the fabric care product is a laundry detergent. Onthe other hand, cationic surfactants are typically employed if thefabric care product is a fabric softener.

Anionic Surfactant

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, or even from about 12 to about 18 carbon atoms.Soaps can be made by direct saponification of fats and oils or by theneutralization of free fatty acids. Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derived from coconutoil and tallow, i.e., sodium or potassium tallow and coconut soap.

Preferred alkyl sulphates are C8-18 alkyl alkoxylated sulphates,preferably a C12-15 alkyl or hydroxyalkyl alkoxylated sulphates.Preferably the alkoxylating group is an ethoxylating group. Typicallythe alkyl alkoxylated sulphate has an average degree of alkoxylationfrom 0.5 to 30 or 20, or from 0.5 to 10. The alkyl group may be branchedor linear. The alkoxylated alkyl sulfate surfactant may be a mixture ofalkoxylated alkyl sulfates, the mixture having an average (arithmeticmean) carbon chain length within the range of about 12 to about 30carbon atoms, or an average carbon chain length of about 12 to about 15carbon atoms, and an average (arithmetic mean) degree of alkoxylation offrom about 1 mol to about 4 mols of ethylene oxide, propylene oxide, ormixtures thereof, or an average (arithmetic mean) degree of alkoxylationof about 1.8 mols of ethylene oxide, propylene oxide, or mixturesthereof. The alkoxylated alkyl sulfate surfactant may have a carbonchain length from about 10 carbon atoms to about 18 carbon atoms, and adegree of alkoxylation of from about 0.1 to about 6 mols of ethyleneoxide, propylene oxide, or mixtures thereof. The alkoxylated alkylsulfate may be alkoxylated with ethylene oxide, propylene oxide, ormixtures thereof. Alkyl ether sulfate surfactants may contain a peakedethoxylate distribution. Specific example include C12-C15 EO 2.5Sulfate, C14-C15 EO 2.5 Sulfate and C12-C15 EO 1.5 Sulfate derived fromNEODOL® alcohols from Shell and C12-C14 EO3 Sulfate, C12-C16 EO3Sulfate, C12-C14 EO2 Sulfate and C12-C₁₄ EO1 Sulfate derived fromnatural alcohols from Huntsman. The AES may be linear, branched, orcombinations thereof. The alkyl group may be derived from synthetic ornatural alcohols such as those supplied by the tradename Neodol® byShell, Safol®, Lial®, and Isalchem® by Sasol or midcut alcohols derivedfrom vegetable oils such as coconut and palm kernel. Another suitableanionic detersive surfactant is alkyl ether carboxylate, comprising aC10-C26 linear or branched, preferably C10-C20 linear, most preferablyC16-C18 linear alkyl alcohol and from 2 to 20, preferably 7 to 13, morepreferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. The acidform or salt form, such as sodium or ammonium salt, may be used, and thealkyl chain may contain one cis or trans double bond. Alkyl ethercarboxylic acids are available from Kao (Akypo®), Huntsman (Empicol®)and Clariant (Emulsogen®).

Other useful anionic surfactants can include the alkali metal salts ofalkyl benzene sulfonates, in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain (linear) or branched chainconfiguration. In some examples, the alkyl group is linear. Such linearalkylbenzene sulfonates are known as “LAS.” In other examples, thelinear alkylbenzene sulfonate may have an average number of carbon atomsin the alkyl group of from about 11 to 14. In a specific example, thelinear straight chain alkylbenzene sulfonates may have an average numberof carbon atoms in the alkyl group of about 11.8 carbon atoms, which maybe abbreviated as C11.8 LAS. Preferred sulphonates are C10-13 alkylbenzene sulphonate. Suitable alkyl benzene sulphonate (LAS) may beobtained, by sulphonating commercially available linear alkyl benzene(LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied bySasol under the tradename Isochem® or those supplied by Petresa underthe tradename Petrelab®, other suitable LAB include high 2-phenyl LAB,such as those supplied by Sasol under the tradename Hyblene®. A suitableanionic detersive surfactant is alkyl benzene sulphonate that isobtained by DETAL catalyzed process, although other synthesis routes,such as HF, may also be suitable. In one aspect a magnesium salt of LASis used. Suitable anionic sulfonate surfactants for use herein includewater-soluble salts of C8-C18 alkyl or hydroxyalkyl sulfonates; C11-C18alkyl benzene sulfonates (LAS), modified alkylbenzene sulfonate (MLAS)as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; methylester sulfonate (MES); and alpha-olefin sulfonate (AOS). Those alsoinclude the paraffin sulfonates may be monosulfonates and/ordisulfonates, obtained by sulfonating paraffins of 10 to 20 carbonatoms. The sulfonate surfactant may also include the alkyl glycerylsulfonate surfactants.

Anionic surfactants of the present invention may exist in an acid form,and said acid form may be neutralized to form a surfactant salt which isdesirable for use in the present detergent compositions. Typical agentsfor neutralization include the metal counterion base such as hydroxides,e.g., NaOH or KOH. Further preferred agents for neutralizing anionicsurfactants of the present invention and adjunct anionic surfactants orcosurfactants in their acid forms include ammonia, amines, oralkanolamines. Alkanolamines are preferred. Suitable non-limitingexamples including monoethanolamine, diethanolamine, triethanolamine,and other linear or branched alkanolamines known in the art; forexample, highly preferred alkanolamines include 2-amino-1-propanol,1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol.

Nonionic Surfactant

Preferably the composition comprises a nonionic detersive surfactant.Suitable nonionic surfactants include alkoxylated fatty alcohols. Thenonionic surfactant may be selected from ethoxylated alcohols andethoxylated alkyl phenols of the formula R(OC2H4),OH, wherein R isselected from the group consisting of aliphatic hydrocarbon radicalscontaining from about 8 to about 15 carbon atoms and alkyl phenylradicals in which the alkyl groups contain from about 8 to about 12carbon atoms, and the average value of n is from about 5 to about 15.Other non-limiting examples of nonionic surfactants useful hereininclude: C8-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactantsfrom Shell; C6-C12 alkyl phenol alkoxylates where the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units, or a mixture thereof;C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C14-C22 mid-chain branched alcohols, BA; C14-C22 mid-chain branchedalkyl alkoxylates, BAE_(X), wherein x is from 1 to 30;alkylpolysaccharides; specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants. Specific example include C12-C15 EO7 and C14-C15 EO7NEODOL® nonionic surfactants from Shell, C12-C14 EO7 and C12-C14 EO9Surfonic® nonionic surfactants from Huntsman.

Highly preferred nonionic surfactants are the condensation products ofGuerbet alcohols with from 2 to 18 moles, preferably 2 to 15, morepreferably 5-9 of ethylene oxide per mole of alcohol. Suitable nonionicsurfactants include those with the trade name Lutensol® from BASF.Lutensol XP-50 is a Guerbet ethoxylate that contains an average of about5 ethoxy groups. Lutensol XP-80 and containing an average of about 8ethoxy groups. Other suitable non-ionic surfactants for use hereininclude fatty alcohol polyglycol ethers, alkylpolyglucosides and fattyacid glucamides, alkylpolyglucosides based on Guerbet alcohols.

Amphoteric Surfactant

The surfactant system may include amphoteric surfactant, such as amineoxide. Preferred amine oxides are alkyl dimethyl amine oxide or alkylamido propyl dimethyl amine oxide, more preferably alkyl dimethyl amineoxide and especially coco dimethyl amino oxide. Amine oxide may have alinear or mid-branched alkyl moiety.

Ampholytic Surfactants

The surfactant system may comprise an ampholytic surfactant. Specific,non-limiting examples of ampholytic surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents may contain at least about 8 carbon atoms, for example fromabout 8 to about 18 carbon atoms, and at least one contains an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 at column 19, lines 18-35, for suitable examples ofampholytic surfactants.

Zwitterionic Surfactant

Zwitterionic surfactants are known in the art, and generally includesurfactants which are neutrally charged overall, but carry at least onepositive charged atom/group and at least one negatively chargedatom/group. Examples of zwitterionic surfactants include: derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678at column 19, line 38 through column 22, line 48, for examples ofzwitterionic surfactants; betaines, including alkyl dimethyl betaine andcocodimethyl amidopropyl betaine, C₈ to C₁₈ (for example from C₁₂ toC₁₈) amine oxides and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylamino-1-propane sulfonate where the alkyl group canbe C₈ to C₁₈ and in certain embodiments from C₁₀ to C₁₄. A preferredzwitterionic surfactant for use in the present invention is thecocoamidopropyl betaine.

Cationic Surfactants

Examples of cationic surfactants include quaternary ammoniumsurfactants, which can have up to 26 carbon atoms specific. Additionalexamples include a) alkoxylate quaternary ammonium (AQA) surfactants asdiscussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethylquaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c)polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003,WO 98/35004, WO 98/35005, and WO 98/35006, which is herein incorporatedby reference; d) cationic ester surfactants as discussed in U.S. Pat.Nos. 4,228,042, 4,239,660 4,260,529 and 6,022,844, which is hereinincorporated by reference; and e) amino surfactants as discussed in U.S.Pat. No. 6,221,825 and WO 00/47708, which is herein incorporated byreference, and specifically amido propyldimethyl amine (APA). Usefulcationic surfactants also include those described in U.S. Pat. No.4,222,905, Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No.4,239,659, Murphy, issued Dec. 16, 1980, both of which are alsoincorporated herein by reference. Quaternary ammonium compounds may bepresent in fabric enhancer compositions, such as fabric softeners, andcomprise quaternary ammonium cations that are positively chargedpolyatomic ions of the structure NR₄ ⁺, where R is an alkyl group or anaryl group.

Adjunct Cleaning Additives

The cleaning compositions of the invention may also contain adjunctcleaning additives. The precise nature of the cleaning adjunct additivesand levels of incorporation thereof will depend on the physical form ofthe cleaning composition, and the precise nature of the cleaningoperation for which it is to be used.

The adjunct cleaning additives may be selected from the group consistingof builders, structurants or thickeners, clay soilremoval/anti-redeposition agents, polymeric soil release agents,polymeric dispersing agents, polymeric grease cleaning agents, enzymes,enzyme stabilizing systems, bleaching compounds, bleaching agents,bleach activators, bleach catalysts, brighteners, dyes, hueing agents,dye transfer inhibiting agents, chelating agents, suds supressors,softeners, and perfumes. This listing of adjunct cleaning additives isexemplary only, and not by way of limitation of the types of adjunctcleaning additives which can be used. In principle, any adjunct cleaningadditive known in the art may be used in the instant invention.

Polymers

The composition may comprise one or more polymers. Non-limitingexamples, all of which may be optionally modified, includepolyethyleneimines, carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates oralkoxylated substituted phenols (ASP). as described in WO 2016/041676.An example of ASP dispersants, include but are not limited to, HOSTAPALBV CONC S1000 available from Clariant.

Polyamines may be used for grease, particulate removal or stain removal.A wide variety of amines and polyaklyeneimines can be alkoxylated tovarious degrees to achieve hydrophobic or hydrophilic cleaning. Suchcompounds may include, but are not limited to, ethoxylatedpolyethyleneimine, ethoxylated hexamethylene diamine, and sulfatedversions thereof. Useful examples of such polymers are HP20 availablefrom BASF or a polymer having the following general structure:

bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)—N+—C_(x)H_(2x)—N+—(CH₃)-bis((C₂H₅O)(C₂H₄O)_(n)),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof. Polypropoxylated-polyethoxylated amphiphilicpolyethyleneimine derivatives may also be included to achieve greatergrease removal and emulsification. These may comprise alkoxylatedpolyalkylenimines, preferably having an inner polyethylene oxide blockand an outer polypropylene oxide block. Detergent compositions may alsocontain unmodified polyethyleneimines useful for enhanced beverage stainremoval. PEI's of various molecular weights are commercially availablefrom the BASF Corporation under the trade name Lupasol® Examples ofsuitable PEI's include, but are not limited to, Lupasol FG®, LupasolG-35®.

The composition may comprise one or more carboxylate polymers, such as amaleate/acrylate random copolymer or polyacrylate homopolymer useful aspolymeric dispersing agents. Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are also useful to provide clay dispersancy.Such materials are described in WO 91/08281. Chemically, these materialscomprise polyacrylates having one ethoxy side-chain per every 7-8acrylate units. The side-chains are of the formula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. The side-chains are esteror ether-linked to the polyacrylate “backbone” to provide a “comb”polymer type structure.

Preferred amphiphilic graft co-polymer(s) comprise (i) polyethyeleneglycol backbone; and (ii) at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. An example ofan amphiphilic graft co-polymer is Sokalan HP22, supplied from BASF.

Alkoxylated substituted phenols as described in WO 2016/041676 are alsosuitable examples of polymers that provide clay dispersancy. Hostapal BVConc S1000, available from Clariant, is one non-limiting example of anASP dispersant.

Preferably the composition comprises one or more soil release polymers.Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN260 SRN300 and SRN325 supplied by Clariant. Other suitable soilrelease polymers are Marloquest polymers, such as Marloquest SL, HSCB,L235M, B, G82 supplied by Sasol. Other suitable soil release polymersinclude methyl-capped ethoxylated propoxylated soil release polymers asdescribed in U.S. Pat. No. 9,365,806.

Preferably the composition comprises one or more polysaccharides whichmay in particular be chosen from carboxymethyl cellulose,methylcarboxymethylcellulose, sulfoethylcellulose,methylhydroxyethylcellulose, carboxymethyl xyloglucan, carboxymethylxylan, sulfoethylgalactomannan, carboxymethyl galactomannan,hydroxyethyl galactomannan, sulfoethyl starch, carboxymethyl starch, andmixture thereof. Other polysaccharides suitable for use in the presentinvention are the glucans. Preferred glucans are Poly alpha-1,3-glucanwhich is a polymer comprising glucose monomeric units linked together byglycosidic linkages (i.e., glucosidic linkages), wherein at least about50% of the glycosidic linkages are alpha-1,3-glycosidic linkages. Polyalpha-1,3-glucan is a type of polysaccharide. Poly alpha-1,3-glucan canbe enzymatically produced from sucrose using one or moreglucosyltransferase enzymes, such as described in U.S. Pat. No.7,000,000, and U.S. Patent Appl. Publ. Nos. 2013/0244288 and2013/0244287 (all of which are incorporated herein by reference), forexample.

Other suitable polysaccharides for use in the composition are cationicpolysaccharides. Examples of cationic polysaccharides include cationicguar gum derivatives, quaternary nitrogen-containing cellulose ethers,and synthetic polymers that are copolymers of etherified cellulose, guarand starch. When used, the cationic polymers herein are either solublein the composition or are soluble in a complex coacervate phase in thecomposition formed by the cationic polymer and the anionic, amphotericand/or zwitterionic surfactant component described hereinbefore.Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418;3,958,581; and U.S. Publication No. 2007/0207109A1.

Polymers can also function as deposition aids for other detergent rawmaterials. Preferred deposition aids are selected from the groupconsisting of cationic and nonionic polymers. Suitable polymers includecationic starches, cationic hydroxyethylcellulose,polyvinylformaldehyde, locust bean gum, mannans, xyloglucans, tamarindgum, polyethyleneterephthalate and polymers containingdimethylaminoethyl methacrylate, optionally with one or more monomersselected from the group comprising acrylic acid and acrylamide.

Additional Amines

Polyamines are known to improve grease removal. Preferred cyclic andlinear amines for performance are 1,3-bis (methylamine)-cyclohexane,4-methylcyclohexane-1,3-diamine (Baxxodur ECX 210 supplied by BASF) 1,3propane diamine, 1,6 hexane diamine, 1,3 pentane diamine (Dytek EPsupplied by Invista), 2-methyl 1,5 pentane diamine (Dytek A supplied byInvista). U.S. Pat. No. 6,710,023 discloses hand dishwashingcompositions containing said diamines and polyamines containing at least3 protonable amines. Polyamines according to the invention have at leastone pka above the wash pH and at least two pka's greater than about 6and below the wash pH. Preferred polyamines with are selected from thegroup consisting of tetraethylenepentamine, hexaethylhexamine,heptaethylheptamines, octaethyloctamines, nonethylnonamines, andmixtures thereof commercially available from Dow, BASF and Huntman.Especially preferred polyetheramines are lipophilic modified asdescribed in U.S. Pat. Nos. 9,752,101, 9,487,739, 9,631,163

Dye Transfer Inhibitor (DTI)

The composition may comprise one or more dye transfer inhibiting agents.In one embodiment of the invention the inventors have surprisingly foundthat compositions comprising polymeric dye transfer inhibiting agents inaddition to the specified dye give improved performance. This issurprising because these polymers prevent dye deposition. Suitable dyetransfer inhibitors include, but are not limited to,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof. Suitable examples includePVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromabondS-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, SokalanHP53, Sokalan HP59, Sokalan® HP 56K, Sokalan® HP 66 from BASF. Othersuitable DTIs are as described in WO2012/004134. When present in asubject composition, the dye transfer inhibiting agents may be presentat levels from about 0.0001% to about 10%, from about 0.01% to about 5%or even from about 0.1% to about 3% by weight of the composition.

Enzymes

Enzymes may be included in the cleaning compositions for a variety ofpurposes, including removal of protein-based, carbohydrate-based, ortriglyceride-based stains from substrates, for the prevention of refugeedye transfer in fabric laundering, and for fabric restoration. Suitableenzymes include proteases, amylases, lipases, carbohydrases, cellulases,oxidases, peroxidases, mannanases, and mixtures thereof of any suitableorigin, such as vegetable, animal, bacterial, fungal, and yeast origin.Other enzymes that may be used in the cleaning compositions describedherein include hemicellulases, peroxidases, proteases, cellulases,endoglucanases, xylanases, lipases, phospholipases, amylases,gluco-amylases, xylanases, esterases, cutinases, pectinases,keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases,or mixtures thereof, esterases, mannanases, pectate lyases, and ormixtures thereof. Other suitable enzymes include Nuclease enzyme. Thecomposition may comprise a nuclease enzyme. The nuclease enzyme is anenzyme capable of cleaving the phosphodiester bonds between thenucleotide sub-units of nucleic acids. The nuclease enzyme herein ispreferably a deoxyribonuclease or ribonuclease enzyme or a functionalfragment thereof. Enzyme selection is influenced by factors such aspH-activity and/or stability optima, thermostability, and stability toactive detergents, builders, and the like.

The enzymes may be incorporated into the cleaning composition at levelsfrom 0.0001% to 5% of active enzyme by weight of the cleaningcomposition. The enzymes can be added as a separate single ingredient oras mixtures of two or more enzymes.

In some embodiments, lipase may be used. Lipase may be purchased underthe trade name Lipex from Novozymes (Denmark). Amylases (Natalase®,Stainzyme®, Stainzyme Plus®) may be supplied by Novozymes, Bagsvaerd,Denmark. Proteases may be supplied by Genencor International, Palo Alto,Calif., USA (e.g. Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark(e.g. Liquanase®, Coronase®, Savinase®). Other preferred enzymes includepectate lyases preferably those sold under the trade names Pectawash®,Xpect®, Pectaway® and the mannanases sold under the trade namesMannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite®(Genencor International Inc., Palo Alto, Calif.). A range of enzymematerials and means for their incorporation into synthetic cleaningcompositions is disclosed in WO 9307263 A; WO 9307260 A; WO 8908694 A;U.S. Pat. Nos. 3,553,139; 4,101,457; and 4,507,219. Enzyme materialsuseful for liquid cleaning compositions, and their incorporation intosuch compositions, are disclosed in U.S. Pat. No. 4,261,868.

Enzyme Stabilizing System

The enzyme-containing compositions described herein may optionallycomprise from about 0.001% to about 10%, in some examples from about0.005% to about 8%, and in other examples, from about 0.01% to about 6%,by weight of the composition, of an enzyme stabilizing system. Theenzyme stabilizing system can be any stabilizing system which iscompatible with the detersive enzyme. Such a system may be inherentlyprovided by other formulation actives, or be added separately, e.g., bythe formulator or by a manufacturer of detergent-ready enzymes. Suchstabilizing systems can, for example, comprise calcium ion, boric acid,propylene glycol, short chain carboxylic acids, boronic acids, chlorinebleach scavengers and mixtures thereof, and are designed to addressdifferent stabilization problems depending on the type and physical formof the cleaning composition. See U.S. Pat. No. 4,537,706 for a review ofborate stabilizers.

Chelating Agent.

Preferably the composition comprises chelating agents and/or crystalgrowth inhibitor. Suitable molecules include copper, iron and/ormanganese chelating agents and mixtures thereof. Suitable moleculesinclude aminocarboxylates, aminophosphonates, succinates, salts thereof,and mixtures thereof. Non-limiting examples of suitable chelants for useherein include ethylenediaminetetracetates,N-(hydroxyethyl)-ethylene-diamine-triacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethylene-tetraamine-hexacetates,diethylenetriamine-pentaacetates, ethanoldiglycines,ethylenediaminetetrakis (methylenephosphonates), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate(EDDS), hydroxyethanedimethylenephosphonic acid (HEDP),methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid(DTPA), and 1,2-dihydroxybenzene-3,5-disulfonic acid (Tiron), saltsthereof, and mixtures thereof. Tiron as well as other sulphonatedcatechols may also be used as effective heavy metal chelants. Othernon-limiting examples of chelants of use in the present invention arefound in U.S. Pat. Nos. 7,445,644, 7,585,376 and 2009/0176684A1. Othersuitable chelating agents for use herein are the commercial DEQUESTseries, and chelants from Monsanto, DuPont, and Nalco Inc.

Brighteners

Optical brighteners or other brightening or whitening agents may beincorporated at levels of from about 0.01% to about 1.2%, by weight ofthe composition, into the cleaning compositions described herein.Commercial optical brighteners, which may be used herein, can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents. Examplesof such brighteners are disclosed in “The Production and Application ofFluorescent Brightening Agents,” M. Zahradnik, John Wiley & Sons, NewYork (1982). Specific, non-limiting examples of optical brightenerswhich may be useful in the present compositions are those identified inU.S. Pat. Nos. 4,790,856 and 3,646,015. Highly preferred Brightenersinclude Disodium4,4′-bis{[4-anilino-6-[bis(2-hydroxyethyl)amino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,Disodium4,4″-bis[(4,6-di-anilino-s-triazin-2-yl)-amino]-2,2′-stilbenedisulfonateand disodium 4,4′-bis-(2-sulfostyryl)biphenyl.

Bleaching Agents.

It may be preferred for the composition to comprise one or morebleaching agents. Suitable bleaching agents include photobleaches,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof.

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonatedaluminium phthalocyanines, xanthene dyes and mixtures thereof;

(2) pre-formed peracids: Suitable preformed peracids include, but arenot limited to compounds selected from the group consisting ofpre-formed peroxyacids or salts thereof typically a percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, for example, Oxone®, and mixturesthereof. Suitable examples include peroxycarboxylic acids or saltsthereof, or peroxysulphonic acids or salts thereof. Particularlypreferred peroxyacids are phthalimido-peroxy-alkanoic acids, inparticular ε-phthalimido peroxy hexanoic acid (PAP). Preferably, theperoxyacid or salt thereof has a melting point in the range of from 30°C. to 60° C.

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof.

Fabric Shading Dyes

The fabric shading dye (sometimes referred to as hueing, bluing orwhitening agents) typically provides a blue or violet shade to fabric.Such dye(s) are well known in the art and may be used either alone or incombination to create a specific shade of hueing and/or to shadedifferent fabric types. The fabric shading dye may be selected from anychemical class of dye as known in the art, including but not limited toacridine, anthraquinone (including polycyclic quinones), azine, azo(e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), benzodifurane,benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,diphenylmethane, formazan, hemicyanine, indigoids, methane,naphthalimides, naphthoquinone, nitro, nitroso, oxazine, phthalocyanine,pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenesand mixtures thereof. The amount of adjunct fabric shading dye presentin a laundry care composition of the invention is typically from 0.0001to 0.05 wt % based on the total cleaning composition, preferably from0.0001 to 0.005 wt %. Based on the wash liquor, the concentration offabric shading dye typically is from 1 ppb to 5 ppm, preferably from 10ppb to 500 ppb.

Suitable fabric shading dyes include small molecule dyes, polymeric dyesand dye-clay conjugates. Preferred fabric shading dyes are selected fromsmall molecule dyes and polymeric dyes. Suitable small molecule dyes maybe selected from the group consisting of dyes falling into the ColourIndex (C.I., Society of Dyers and Colourists, Bradford, UK)classifications of Acid, Direct, Basic, Reactive, Solvent or Dispersedyes.

Suitable polymeric dyes include dyes selected from the group consistingof polymers containing covalently bound (sometimes referred to asconjugated) chromogens, (also known as dye-polymer conjugates), forexample polymers with chromogen monomers co-polymerized into thebackbone of the polymer and mixtures thereof. Preferred polymeric dyescomprise the optionally substituted alkoxylated dyes, such asalkoxylated triphenyl-methane polymeric colourants, alkoxylatedcarbocyclic and alkoxylated heterocyclic azo colourants includingalkoxylated thiophene polymeric colourants, and mixtures thereof, suchas the fabric-substantive colorants sold under the name of Liquitint®(Milliken, Spartanburg, S.C., USA).

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay; a preferred clay may be selected from the group consisting ofMontmorillonite clay, Hectorite clay, Saponite clay and mixturesthereof.

Pigments are well known in the art and may also be used in the laundrycare compositions herein. Suitable pigments include C.I Pigment Blues 15to 20, especially 15 and/or 16, C.I. Pigment Blue 29, C.I. PigmentViolet 15, Monastral Blue and mixtures thereof.

Builders

The cleaning compositions of the present invention may optionallycomprise a builder. Builders selected from aluminosilicates andsilicates assist in controlling mineral hardness in wash water, or toassist in the removal of particulate soils from surfaces. Suitablebuilders may be selected from the group consisting of phosphatespolyphosphates, especially sodium salts thereof; carbonates,bicarbonates, sesquicarbonates, and carbonate minerals other than sodiumcarbonate or sesquicarbonate; organic mono-, di-, tri-, andtetracarboxylates, especially water-soluble non-surfactant carboxylatesin acid, sodium, potassium or alkanolammonium salt form, as well asoligomeric or water-soluble low molecular weight polymer carboxylatesincluding aliphatic and aromatic types; and phytic acid. These may becomplemented by borates, e.g., for pH-buffering purposes, or bysulfates, especially sodium sulfate and any other fillers or carrierswhich may be important to the engineering of stable surfactant and/orbuilder-containing cleaning compositions.

pH Buffer System

The compositions may also include a pH buffer system. The cleaningcompositions herein may be formulated such that, during use in aqueouscleaning operations, the wash water will have a pH of between about 6.0and about 12, and in some examples, between about 7.0 and 11. Techniquesfor controlling pH at recommended usage levels include the use ofbuffers, alkalis, or acids, and are well known to those skilled in theart. These include, but are not limited to, the use of sodium carbonate,citric acid or sodium citrate, monoethanol amine or other amines, boricacid or borates, and other pH-adjusting compounds well known in the art.The cleaning compositions herein may comprise dynamic in-wash pHprofiles by delaying the release of citric acid.

Structurant/Thickeners

Structured liquids can either be internally structured, whereby thestructure is formed by primary ingredients (e.g. surfactant material)and/or externally structured by providing a three dimensional matrixstructure using secondary ingredients (e.g. polymers, clay and/orsilicate material). The composition may comprise from about 0.01% toabout 5%, by weight of the composition, of a structurant, and in someexamples, from about 0.1% to about 2.0%, by weight of the composition,of a structurant. The structurant may be selected from the groupconsisting of diglycerides and triglycerides, ethylene glycoldistearate, microcrystalline cellulose, cellulose-based materials,microfiber cellulose, biopolymers, xanthan gum, gellan gum, and mixturesthereof. In some examples, a suitable structurant includes hydrogenatedcastor oil, and non-ethoxylated derivatives thereof. Other suitablestructurants are disclosed in U.S. Pat. No. 6,855,680. Such structurantshave a thread-like structuring system having a range of aspect ratios.Further suitable structurants and the processes for making them aredescribed in WO 2010/034736.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the cleaning compositions described herein. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos.4,489,455, 4,489,574, and in front-loading style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds suppressors include monocarboxylic fatty acid, and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols. Sudssuppressors are described in U.S. Pat. Nos. 2,954,347; 4,075,118;4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471;4,983,316; 5,288,431; 4,639,489; 4,749,740; and 4,798,679.

The cleaning compositions herein may comprise from 0% to about 10%, byweight of the composition, of suds suppressor. When utilized as sudssuppressors, monocarboxylic fatty acids, and salts thereof, may bepresent in amounts up to about 5% by weight of the cleaning composition,and in some examples, may be from about 0.5% to about 3% by weight ofthe cleaning composition. Silicone suds suppressors may be utilized inamounts up to about 2.0% by weight of the cleaning composition, althoughhigher amounts may be used. Monostearyl phosphate suds suppressors maybe utilized in amounts ranging from about 0.1% to about 2% by weight ofthe cleaning composition. Hydrocarbon suds suppressors may be utilizedin amounts ranging from about 0.01% to about 5.0% by weight of thecleaning composition, although higher levels can be used. Alcohol sudssuppressors may be used at about 0.2% to about 3% by weight of thecleaning composition.

Suds Boosters

If high sudsing is desired, suds boosters such as the C10-C16alkanolamides may be incorporated into the cleaning compositions fromabout 1% to about 10% by weight of the cleaning composition. Someexamples include the C10-C14 monoethanol and diethanol amides. Ifdesired, water-soluble magnesium and/or calcium salts such as MgCl₂,MgSO₄, CaCl₂, CaSO₄, and the like, may be added at levels of about 0.1%to about 2% by weight of the cleaning composition, to provide additionalsuds and to enhance grease removal performance.

Fillers and Carriers

Fillers and carriers may be used in the cleaning compositions describedherein. As used herein, the terms “filler” and “carrier” have the samemeaning and can be used interchangeably. Liquid cleaning compositions,and other forms of cleaning compositions that include a liquid component(such as liquid-containing unit dose cleaning compositions), may containwater and other solvents as fillers or carriers. Low molecular weightprimary or secondary alcohols exemplified by methanol, ethanol,propanol, isopropanol, and phenoxyethanol are suitable. Monohydricalcohols may be used in some examples for solubilizing surfactants, andpolyols such as those containing from 2 to about 6 carbon atoms and from2 to about 6 hydroxy groups (e.g., 1,2-propanediol, 1,3-propanediol,2,3-butanediol, ethylene glycol, and glycerine may be used).Amine-containing solvents may also be used.

Methods of Use

The present invention includes methods for whitening fabric. Compactfluid detergent compositions that are suitable for sale to consumers aresuited for use in laundry pretreatment applications, laundry cleaningapplications, and home care applications. Such methods include, but arenot limited to, the steps of contacting detergent compositions in neatform or diluted in wash liquor, with at least a portion of a fabricwhich may or may not be soiled and then optionally rinsing the fabric.The fabric material may be subjected to a washing step prior to theoptional rinsing step. Machine laundry methods may comprise treatingsoiled laundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. An “effectiveamount” of the detergent composition means from about 20 g to about 300g of product dissolved or dispersed in a wash solution of volume fromabout 5 L to about 65 L. The water temperatures may range from about 5°C. to about 100° C. The water to soiled material (e.g., fabric) ratiomay be from about 1:1 to about 30:1. The compositions may be employed atconcentrations of from about 500 ppm to about 15,000 ppm in solution. Inthe context of a fabric laundry composition, usage levels may also varydepending not only on the type and severity of the soils and stains, butalso on the wash water temperature, the volume of wash water, and thetype of washing machine (e.g., top-loading, front-loading, vertical-axisJapanese-type automatic washing machine).

The detergent compositions herein may be used for laundering of fabricsat reduced wash temperatures. These methods of laundering fabriccomprise the steps of delivering a laundry detergent composition towater to form a wash liquor and adding a laundering fabric to said washliquor, wherein the wash liquor has a temperature of from about 0° C. toabout 20° C., or from about 0° C. to about 15° C., or from about 0° C.to about 9° C. The fabric may be contacted to the water prior to, orafter, or simultaneous with, contacting the laundry detergentcomposition with water. Another method includes contacting a nonwovensubstrate, which is impregnated with the detergent composition, with asoiled material. As used herein, “nonwoven substrate” can comprise anyconventionally fashioned nonwoven sheet or web having suitable basisweight, caliper (thickness), absorbency, and strength characteristics.Non-limiting examples of suitable commercially available nonwovensubstrates include those marketed under the trade names SONTARA® byDuPont and POLY WEB® by James River Corp.

Hand washing/soak methods, and combined hand washing with semi-automaticwashing machines, are also included.

Packaging for the Compositions

The cleaning compositions described herein can be packaged in anysuitable container including those constructed from paper, cardboard,plastic materials, and any suitable laminates. An optional packagingtype is described in European Application No. 94921505.7.

Multi-Compartment Pouch

The cleaning compositions described herein may also be packaged as amulti-compartment cleaning composition.

Other Adjunct Ingredients

A wide variety of other ingredients may be used in the cleaningcompositions herein, including, for example, other active ingredients,carriers, hydrotropes, processing aids, dyes or pigments, solvents forliquid formulations, solid or other liquid fillers, erythrosine,colloidal silica, waxes, probiotics, surfactin, aminocellulosicpolymers, Zinc Ricinoleate, perfume microcapsules, rhamnolipids,sophorolipids, glycopeptides, methyl ester ethoxylates, sulfonatedestolides, cleavable surfactants, biopolymers, silicones, modifiedsilicones, aminosilicones, deposition aids, hydrotropes (especiallycumene-sulfonate salts, toluene-sulfonate salts, xylene-sulfonate salts,and naphalene salts), PVA particle-encapsulated dyes or perfumes,pearlescent agents, effervescent agents, color change systems, siliconepolyurethanes, opacifiers, tablet disintegrants, biomass fillers,fast-dry silicones, glycol distearate, starch perfume encapsulates,emulsified oils including hydrocarbon oils, polyolefins, and fattyesters, bisphenol antioxidants, micro-fibrous cellulose structurants,properfumes, styrene/acrylate polymers, triazines, soaps, superoxidedismutase, benzophenone protease inhibitors, functionalized TiO2,dibutyl phosphate, silica perfume capsules, and other adjunctingredients, choline oxidase, triarylmethane blue and violet basic dyes,methine blue and violet basic dyes, anthraquinone blue and violet basicdyes, azo dyes basic blue 16, basic blue 65, basic blue 66 basic blue67, basic blue 71, basic blue 159, basic violet 19, basic violet 35,basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nileblue A and xanthene dye basic violet 10, an alkoxylated triphenylmethanepolymeric colorant; an alkoxylated thiopene polymeric colorant;thiazolium dye, mica, titanium dioxide coated mica, bismuth oxychloride,and other actives.

Anti-oxidant: The composition may optionally contain an anti-oxidantpresent in the composition from about 0.001 to about 2% by weight.Preferably the antioxidant is present at a concentration in the range0.01 to 0.08% by weight. Mixtures of anti-oxidants may be used.

One class of anti-oxidants used in the present invention is alkylatedphenols. Hindered phenolic compounds are a preferred type of alkylatedphenols having this formula. A preferred hindered phenolic compound ofthis type is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

Furthermore, the anti-oxidant used in the composition may be selectedfrom the group consisting of α-, β-, γ-, δ-tocopherol, ethoxyquin,2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl hydroquinone,tert-butyl hydroxyanisole, lignosulphonic acid and salts thereof, andmixtures thereof.

The cleaning compositions described herein may also contain vitamins andamino acids such as: water soluble vitamins and their derivatives, watersoluble amino acids and their salts and/or derivatives, water insolubleamino acids viscosity modifiers, dyes, nonvolatile solvents or diluents(water soluble and insoluble), pearlescent aids, pediculocides, pHadjusting agents, preservatives, skin active agents, sunscreens, UVabsorbers, niacinamide, caffeine, and minoxidil.

The cleaning compositions of the present invention may also containpigment materials such as nitroso, monoazo, disazo, carotenoid,triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine,anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine,botanical, and natural colors, including water soluble components suchas those having C.I. Names.

The cleaning compositions of the present invention may also containantimicrobial agents. Cationic active ingredients may include but arenot limited to n-alkyl dimethyl benzyl ammonium chloride, alkyl dimethylethyl benzyl ammonium chloride, dialkyl dimethyl quaternary ammoniumcompounds such as didecyl dimethyl ammonium chloride,N,N-didecyl-Nmethyl-poly(oxyethyl) ammonium propionate, dioctyl didecylammonium chloride, also including quaternary species such asbenzethonium chloride and quaternary ammonium compounds with inorganicor organic counter ions such as bromine, carbonate or other moietiesincluding dialkyl dimethyl ammonium carbonates, as well as antimicrobialamines such as Chlorhexidine Gluconate, PHMB (Polyhexamethylenebiguanide), salt of a biguanide, a substituted biguanide derivative, anorganic salt of a quaternary ammonium containing compound or aninorganic salt of a quaternary ammonium containing compound or mixturesthereof.

In one aspect, such method comprises the steps of optionally washingand/or rinsing said surface or fabric, contacting said surface or fabricwith any composition disclosed in this specification then optionallywashing and/or rinsing said surface or fabric is disclosed, with anoptional drying step.

Drying of such surfaces or fabrics may be accomplished by any one of thecommon means employed either in domestic or industrial settings. Thefabric may comprise any fabric capable of being laundered in normalconsumer or institutional use conditions, and the invention is suitablefor cellulosic substrates and in some aspects also suitable forsynthetic textiles such as polyester and nylon and for treatment ofmixed fabrics and/or fibers comprising synthetic and cellulosic fabricsand/or fibers. As examples of synthetic fabrics are polyester, nylon,these may be present in mixtures with cellulosic fibers, for example,polycotton fabrics. The solution typically has a pH of from 7 to 11,more usually 8 to 10.5. The compositions are typically employed atconcentrations from 500 ppm to 5,000 ppm in solution. The watertemperatures typically range from about 5° C. to about 90° C. The waterto fabric ratio is typically from about 1:1 to about 30:1.

Thus, in a third embodiment, the invention provides a method of treatinga textile. The method preferably comprises the steps of (i) treating atextile with an aqueous solution containing a leuco composition asdescribed herein, (ii) optionally, rinsing the textile, and (iii) dryingthe textile. In one aspect, the invention provides a method of treatinga textile comprising the steps of: (i) treating a textile with anaqueous solution containing a leuco composition as described herein, theaqueous solution comprising from 10 ppb to 5000 ppm of at least onereactive leuco compound and from 0.0 g/L to 3 g/L of a surfactant; (ii)optionally rinsing; and (iii) drying the textile. The leuco compositionand/or reactive leuco colorant utilized in this method can be any of theleuco compositions and reactive leuco colorants described herein.Further, the aqueous solution utilized in the method can be created byadding a leuco composition directly to an aqueous medium or by adding alaundry care composition containing a leuco composition to an aqueousmedium.

EXAMPLES

Preparation of Leuco Monomers

Leuco alcohol 3: A solution of 4,4′-bis(dimethylamino)benzhydrol (1)(0.27 g, 1.0 mmol), 2-(methylphenylamino)ethanol (2) (0.18 g, 1.2 mmol),and p-toluenesulfonic acid (pTSA) monohydrate (0.76 g, 4 mmol) inmethanol (25 mL) is stirred at reflux with a Dean-Stark trap for 9 h.The mixture is diluted with methylene chloride and washed three timeswith aq. sodium bicarbonate. The organic layer is dried over anhydrousMgSO₄ and filtered. The filtrate is concentrated in vacuo to give aresidue which is purified by column chromatography on silica gel (1:1ethyl acetate/hexane) to yield the leuco alcohol intermediate 3.

Preparation of Reactive Leuco Compounds

Reactive Leuco 4: A solution of dry toluene (10 mL) and diphosgene (0.4g, 2.0 mmol) is cooled to 0-5° C. in an ice bath. A solution ofintermediate 3 (1.05 g, 2.55 mmol) and triethylamine (0.77 g, 7.65 mmol)in dry toluene (15 mL) is added dropwise to the diphosgene solution over15 minutes, keeping the temperature <5° C. The reaction mixture isallowed to react at 0-5° C. for 4 hours, then allowed to warm to roomtemperature overnight. The toluene is removed on the rotovap to drynessto yield reactive leuco 4.

Reactive Leuco 5: To a solution of intermediate 3 (5.0 g, 12.4 mmol) indichloromethane (30 mL) at 0-5° C. is added triethylamine (1.25 g, 12.4mmol) followed by the slow addition of p-toluenesulfonyl chloride (2.4g, 12.6 mmol). The reaction mixture is allowed to warm to roomtemperature overnight. Reaction progress is monitored by TLC (2:1EtOAc/MeOH). Once complete, the reaction mixture is diluted with water(50 mL) and then 10% sodium bicarbonate solution (50 mL) is added. Thelayers are separated and the aqueous is extracted twice with1,2-dichloroethane. The combined organic layers are washed with water,dried (Na₂SO₄), filtered and concentrated to yield reactive leuco 5.

Reactive Leuco 6: To 80 mL of acetone in 250 mL four neck flask fittedwith stirrer temperature probe, dropping funnel and N₂ outlet, cyanuricchloride (6.35 g, 0.035 mole) was charged. The solution mixture washeated at 70° C. for 45 minutes to dissolve and subsequently cooled to 0to 10° C. A dropwise solution of 3 (10.0 g, 0.025 mole in 40 mL ofacetone) was added to the reaction mixture. After addition, the reactionwas allowed to stir at room temperature for 4 hours and then refluxedfor one hour and left at room temperature overnight. TLC indicatedformation of product. The reaction mixture was filtered and solid wascollected. Product was characterized by NMR and mass spectrometry m/zpeak at 550 and 551.

Reactive Leuco 7: Compound 3 (10.0 g, 0.025 mole) was added toacetonitrile (60 mL) and THF (10 mL) in 150 mL 3-neck flask fitted withstirrer, temperature probe, and N₂ outlet. To the reaction flasksulfamic acid. (5.05 g, 0.052 mole) was added and the reaction mixturewas heated at 70° C. for 10 hours. The reaction mixture was filtered andthe excess solvent was removed in rotory evaporator. The product wascharacterized using NMR and mass spectrometry m/z at 483.

Application Example

Reactive Leuco compounds 6 and 7, along with a hydrolyzed form of each(structure 8 and structure 3 above, respectively), were tested forability to deliver a whiteness benefit increase as described in Method Ibelow with the following changes: (a) Two swatches of MultiFiber Fabric(MFF41, TestFabrics, Inc. West Pittston, Pa.) were used per flask; (b)The base wash solution is dosed with the leuco compound stock to achievea wash solution with a concentration of 5.0×10⁻⁶ mole/L; (c) L*, a*, b*and Whiteness Index (WI CIE) values for the cotton, nylon and polyestersections of the MFF41 fabric swatches were measured on the dry swatches24 hours following the drying procedure using a color spectrophotometer(X-rite Color i7) with reflectance mode (UV light excluded). Thecalculated values of δΔWI CIE at 24 hours are given in the table belowfor each of the three fabrics.

Leuco Compound Cotton Nylon Polyester 6 1.22 −0.09 1.40 8 1.45 0.01 1.137 4.34 1.44 1.20 3 3.87 0.18 1.87

The data show each leuco material delivers an improvement in the WI CIEvalue on cotton and polyester relative to the nil-leuco control. Inaddition, benefits are observed for some samples on nylon.

Test Methods

Fabric swatches used in the test methods herein are obtained fromTestfabrics, Inc. West Pittston, Pa., and are 100% Cotton, Style 403(cut to 2″×2″) and/or Style 464 (cut to 4″×6″), and an unbrightenedmultifiber fabric, specifically Style 41 (5 cm×10 cm).

All reflectance spectra and color measurements, including L*, a*, b*,K/S, and Whiteness Index (WI CIE) values on dry fabric swatches, aremade using one of four spectrophotometers: (1) a Konica-Minolta 3610dreflectance spectrophotometer (Konica Minolta Sensing Americas, Inc.,Ramsey, N.J., USA; D65 illumination, 10° observer, UV light excluded),(2) a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, Va.;D65 illumination, 10° observer, UV light excluded), (3) a Color-Eye®7000A (GretagMacbeth, New Windsor, N.Y., USA; D65 light, UV excluded),or (4) a Color i7 spectrophotometer (X-rite, Inc., Grand Rapids, Mich.,USA; D65 light, UV excluded).

Where fabrics are irradiated, unless otherwise indicated, the specifiedfabrics post-dry are exposed to simulated sunlight with irradiance of0.77 W/m² @ 420 nm in an Atlas Xenon Fade-Ometer Ci3000+ (Atlas MaterialTesting Technology, Mount Prospect, Ill., USA) equipped with Type SBorosilicate inner (Part no. 20277300) and outer (Part no. 20279600)filters, set at 37° C. maximum cabinet temperature, 57° C. maximum blackpanel temperature (BPT black panel geometry), and 35% RH (relativehumidity). Unless otherwise indicated, irradiation is continuous overthe stated duration.

I. Method for Determining Leuco Compound Efficiency from a Wash Solution

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution). A concentrated stock solution of eachleuco compound to be tested is prepared in a solvent selected fromethanol or 50:50 ethanol:water, preferably ethanol.

A base wash solution is prepared by dissolving heavy duty liquid laundrydetergent nil brightener (5.23 g/1.0 L) in deionized water. Fourstripped cotton swatches are weighed together and placed in a 250 mLErlenmeyer flask along with two 10 mm glass marbles. A total of threesuch flasks are prepared for each wash solution to be tested. The basewash solution is dosed with the leuco compound stock to achieve a washsolution with the desired 1.0 ppm wash concentration of the leucocompound.

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburg, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours.

A. Dark Conditions Post-Dry

L*, a*, b* and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches 48 hours following the drying procedureusing a LabScan XE reflectance spectrophotometer. The L*, a*, and b*values of the 12 swatches generated for each leuco compound (threeflasks with four swatches each) are averaged and the leuco compoundefficiency (LCE) of each leuco compound is calculated using thefollowing equation:LCE=DE*=[(L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²]^(1/2)wherein the subscripts c and s respectively refer to the control, i.e.,the fabric washed in detergent with no leuco compound, and the sample,i.e., the fabric washed in detergent containing leuco compound.

The WI CIE values of the 12 swatches generated for each wash solution(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:ΔWI=WI CIE (after wash)−WI CIE (before wash)

B. Light Conditions Post-Dry

Because consumer habits vary greatly throughout the world, the methodsused must allow for the possibility of measuring the benefits of leucocompounds across conditions. One such condition is the exposure to lightfollowing drying. Some leuco compounds will not exhibit as large abenefit under dark storage as under light storage, so each leucocompound must be tested under both sets of conditions to determine theoptimum benefit. Therefore Method I includes exposure of the driedfabrics to simulated sunlight for various increments of time beforemeasurements are taken, and the LCE value is set to the maximum valueobtained from the set of exposure times described below.

The specified cotton fabrics post-dry are exposed to simulated sunlightfor 15 min, 30 min, 45 min, 60 min, 75 min, 90 min, 120 min, and 240min. The L*, a*, b* and Whiteness Index (WI CIE) values for the cottonfabrics are measured on the swatches after each exposure period using aLabScan XE reflectance spectrophotometer. The calculation of the LCE andthe ΔWI value at each exposure time point is as described in Method I.A.above, and the LCE value and the ΔWI value for the leuco compound areset to the maximum values obtained from the set of exposure timeslisted.

II. Method for Determining Relative Hue Angle (vs. Nil Leuco Compound)

The relative hue angle delivered by a leuco compound to cotton fabricstreated according to Method I described above is determined as follows.

-   -   a) The a* and b* values of the 12 swatches from each solution        are averaged and the following formulas used to determine Δa*        and Δb*:        Δa*=a* _(s) −a* _(c) and Δb*=b* _(s) −b* _(c)        -   wherein the subscripts c and s respectively refer to the            fabric washed in detergent with no leuco compound and the            fabric washed in detergent containing leuco compound.    -   b) If the absolute value of both Δa* and Δb*<0.25, no Relative        Hue Angle (RHA) is calculated. If the absolute value of either        Δa* or Δb* is ≥0.25, the RHA is determined using one of the        following formulas:        RHA=A TAN 2(Δa*,Δb*) for Δb*≥0        RHA=360+A TAN 2(Δa*,Δb*) for Δb*<0        A relative hue angle can be calculated for each time point where        data is collected in either the dark post-dry or light post-dry        assessments. Any of these points may be used to satisfy the        requirements of a claim.        III. Method for Determining Change in Whiteness Index for a        Laundry Care Formulation

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution).

A base wash solution is prepared by dissolving the laundry careformulation (5.23 g/1.0 L) in deionized water. Four stripped cottonswatches are weighed together and placed in a 250 mL Erlenmeyer flaskalong with two 10 mm glass marbles. A total of three such flasks areprepared.

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburg, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours.

L*, a*, b* and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches, according to Method I.A. and/or I.B.above, using a LabScan XE reflectance spectrophotometer. The WI CIEvalues of the 12 swatches generated for the laundry care formulation(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:ΔWI=WI CIE (after wash)−WI CIE (before wash)

Formulation Examples

The following are illustrative examples of cleaning compositionsaccording to the present disclosure and are not intended to be limiting.

Examples 1-7 Heavy Duty Liquid Laundry Detergent Compositions

1 2 3 4 5 6 7 Ingredients % weight AE_(1.8)S 6.77 5.16 1.36 1.30 — — —AE₃S — — — — 0.45 — — LAS 0.86 2.06 2.72 0.68 0.95 1.56 3.55 HSAS 1.852.63 1.02 — — — — AE9 6.32 9.85 10.20 7.92 AE8 35.45 AE7 8.40 12.44C₁₂₋₁₄ dimethyl Amine Oxide 0.30 0.73 0.23 0.37 — — — C₁₂₋₁₈ Fatty Acid0.80 1.90 0.60 0.99 1.20 — 15.00 Citric Acid 2.50 3.96 1.88 1.98 0.902.50 0.60 Optical Brightener 1 1.00 0.80 0.10 0.30 0.05 0.50 0.001Optical Brightener 3 0.001 0.05 0.01 0.20 0.50 — 1.00 Sodium formate1.60 0.09 1.20 0.04 1.60 1.20 0.20 DTI 0.32 0.05 — 0.60 — 0.60 0.01Sodium hydroxide 2.30 3.80 1.70 1.90 1.70 2.50 2.30 Monoethanolamine1.40 1.49 1.00 0.70 — — — Diethylene glycol 5.50 — 4.10 — — — — Chelant1 0.15 0.15 0.11 0.07 0.50 0.11 0.80 4-formyl-phenylboronic acid — — — —0.05 0.02 0.01 Sodium tetraborate 1.43 1.50 1.10 0.75 — 1.07 — Ethanol1.54 1.77 1.15 0.89 — 3.00 7.00 Polymer 1 0.10 — — — — — 2.00 Polymer 20.30 0.33 0.23 0.17 — — — Polymer 3 — — — — — — 0.80 Polymer 4 0.80 0.810.60 0.40 1.00 1.00 — 1,2-Propanediol — 6.60 — 3.30 0.50 2.00 8.00Structurant 0.10 — — — — — 0.10 Perfume 1.60 1.10 1.00 0.80 0.90 1.501.60 Perfume encapsulate 0.10 0.05 0.01 0.02 0.10 0.05 0.10 Protease0.80 0.60 0.70 0.90 0.70 0.60 1.50 Mannanase 0.07 0.05 0.045 0.06 0.040.045 0.10 Amylase 1 0.30 — 0.30 0.10 — 0.40 0.10 Amylase 2 — 0.20 0.100.15 0.07 — 0.10 Xyloglucanase 0.20 0.10 — — 0.05 0.05 0.20 Lipase 0.400.20 0.30 0.10 0.20 — — Polishing enzyme — 0.04 — — — 0.004 — Nuclease0.05 — — — — — 0.003 Dispersin B — — — 0.05 0.03 0.001 0.001 Liquitint ®V200 0.01 — — — — — 0.005 Leuco compound 0.5 0.35 0.1 0.2 0.04 0.02 0.04Dye control agent — 0.3 — 0.03 — 0.3 0.3 Water, dyes & minors Balance pH8.2 Based on total cleaning and/or treatment composition weight. Enzymelevels are reported as raw material.

Examples 8 to 18 Unit Dose Compositions

These examples provide various formulations for unit dose laundrydetergents. Compositions 8 to 12 comprise a single unit dosecompartment. The film used to encapsulate the compositions ispolyvinyl-alcohol-based film.

8 9 10 11 12 Ingredients % weight LAS 19.09 16.76 8.59 6.56 3.44 AE3S1.91 0.74 0.18 0.46 0.07 AE7 14.00 17.50 26.33 28.08 31.59 Citric Acid0.6 0.6 0.6 0.6 0.6 C12-15 Fatty Acid 14.8 14.8 14.8 14.8 14.8 Polymer 34.0 4.0 4.0 4.0 4.0 Chelant 2 1.2 1.2 1.2 1.2 1.2 Optical Brightener 10.20 0.25 0.01 0.01 0.50 Optical Brightener 2 0.20 — 0.25 0.03 0.01Optical Brightener 3 0.18 0.09 0.30 0.01 — DTI 0.10 — 0.20 — — Glycerol6.1 6.1 6.1 6.1 6.1 Monoethanol amine 8.0 8.0 8.0 8.0 8.0Tri-isopropanol amine — — 2.0 — — Tri-ethanol amine — 2.0 — — — Cumenesulfonate — — — — 2.0 Protease 0.80 0.60 0.07 1.00 1.50 Mannanase 0.070.05 0.05 0.10 0.01 Amylase 1 0.20 0.11 0.30 0.50 0.05 Amylase 2 0.110.20 0.10 — 0.50 Polishing enzyme 0.005 0.05 — — — Nuclease 0.— 0.05 — —0.005 Dispersin B 0.010 0.05 0.005 0.005 — Cyclohexyl dimethanol — — —2.0 — Leuco compound 0.6 0.3 1.0 0.1 0.4 Liquitint ® V200 — — 0.01 0.05— Structurant 0.14 0.14 0.14 0.14 0.14 Perfume 1.9 1.9 1.9 1.9 1.9 Dyecontrol agent 0.1 0.3 0.2 0.5 0.3 Water and miscellaneous To 100% pH7.5-8.2 Based on total cleaning and/or treatment composition weight.Enzyme levels are reported as raw material.

In the following examples the unit dose has three compartments, butsimilar compositions can be made with two, four or five compartments.The film used to encapsulate the compartments is polyvinyl alcohol.

Base compositions 13 14 15 16 Ingredients % weight HLAS 26.82 16.35 7.503.34 AE7 17.88 16.35 22.50 30.06 Citric Acid 0.5 0.7 0.6 0.5 C12-15Fatty acid 16.4 6.0 11.0 13.0 Polymer 1 2.9 0.1 — — Polymer 3 1.1 5.12.5 4.2 Cationic cellulose polymer — — 0.3 0.5 Polymer 6 — 1.5 0.3 0.2Chelant 2 1.1 2.0 0.6 1.5 Optical Brightener 1 0.20 0.25 0.01 0.005Optical Brightener 3 0.18 0.09 0.30 0.005 DTI 0.1 — 0.05 — Glycerol 5.35.0 5.0 4.2 Monoethanolamine 10.0 8.1 8.4 7.6 Polyethylene glycol — —2.5 3.0 Potassium sulfite 0.2 0.3 0.5 0.7 Protease 0.80 0.60 0.40 0.80Amylase 1 0.20 0.20 0.200 0.30 Polishing enzyme — — 0.005 0.005 Nuclease0.05 — — — Dispersin B — 0.010 0.010 0.010 MgCl₂ 0.2 0.2 0.1 0.3Structurant 0.2 0.1 0.2 0.2 Acid Violet 50 0.04 0.03 0.05 0.03Perfume/encapsulates 0.10 0.30 0.01 0.05 Dye control agent 0.2 0.03 0.4— Solvents and misc. To 100% pH 7.0-8.2 Finishing compositions 17 18Compartment A B C A B C Volume of each compartment 40 ml 5 ml 5 ml 40 ml5 ml 5 ml Ingredients Active material in Wt. % Perfume 1.6 1.6 1.6 1.61.6 1.6 Liquitint ® V200 0 0.006 0 0 0.004 — Leuco compound 0.2 0.4 — —TiO2 — — 0.1 — 0.1 Sodium Sulfite 0.4 0.4 0.4 0.1 0.3 0.3 Polymer 5 — 2— — Hydrogenated castor oil 0.14 0.14 0.14 0.14 0.14 0.14 BaseComposition 13, 14, 15 Add to 100% or 16 Based on total cleaning and/ortreatment composition weight, enzyme levels are reported as rawmaterial.

AE1.8S is C₁₂₋₁₅ alkyl ethoxy (1.8) sulfate AE3S is C₁₂₋₁₅ alkyl ethoxy(3) sulfate AE7 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree ofethoxylation of 7 AE8 is C₁₂₋₁₃ alcohol ethoxylate, with an averagedegree of ethoxylation of 8 AE9 is C₁₂₋₁₃ alcohol ethoxylate, with anaverage degree of ethoxylation of 9 Amylase 1 is Stainzyme ®, 15 mgactive/g, supplied by Novozymes Amylase 2 is Natalase ®, 29 mg active/g,supplied by Novozymes Xyloglucanase is Whitezyme ®, 20 mg active/g,supplied by Novozymes Chelant 1 is diethylene triamine pentaacetic acidChelant 2 is 1-hydroxyethane 1,1-diphosphonic acid Dispersin B is aglycoside hydrolase, reported as 1000 mg active/g DTI is eitherpoly(4-vinylpyridine-1-oxide) (such as Chromabond S- 403E ®), orpoly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as Sokalan HP56 ®).Dye control agent Dye control agent in accordance with the invention,for example Suparex ® O.IN (M1), Nylofixan ® P (M2), Nylofixan ® PM(M3), or Nylofixan ® HF (M4) HSAS is mid-branched alkyl sulfate asdisclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443 LAS islinear alkylbenzenesulfonate having an average aliphatic carbon chainlength C₉-C₁₅ (HLAS is acid form). Leuco colorant Any suitable leucocolorant or mixtures thereof according to the instant invention. Lipaseis Lipex ®, 18 mg active/g, supplied by Novozymes Liquitint ® V200 is athiophene azo dye provided by Milliken Mannanase is Mannaway ®, 25 mgactive/g, supplied by Novozymes Nuclease is a Phosphodiesterase SEQ IDNO 1, reported as 1000 mg active/g Optical Brightener 1 is disodium4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate Optical Brightener 2 is disodium4,4′-bis-(2-sulfostyryl)biphenyl (sodium salt) Optical Brightener 3 isOptiblanc SPL10 ® from 3V Sigma Perfume encapsulate is a core-shellmelamine formaldehyde perfume microcapsules. Polishing enzyme isPara-nitrobenzyl esterase, reported as 1000 mg active/g Polymer 1 isbis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)- bis((C₂H₅O)(C₂H₄O)n),wherein n = 20-30, x = 3 to 8 or sulphated or sulfonated variantsthereof Polymer 2 is ethoxylated (EO₁₅) tetraethylene pentamine Polymer3 is ethoxylated polyethylenimine Polymer 4 is ethoxylated hexamethylenediamine Polymer 5 is Acusol 305, provided by Rohm&Haas Polymer 6 is apolyethylene glycol polymer grafted with vinyl acetate side chains,provided by BASF. Protease is Purafect Prime ®, 40.6 mg active/g,supplied by DuPont Structurant is Hydrogenated Castor Oil

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

We claim:
 1. A leuco composition comprising at least one reactive leucocompound, wherein the reactive leuco compound comprises a leuco moietyand at least one reactive moiety covalently bound to the leuco moiety,wherein the reactive moiety is sufficiently electrophilic to react witha nucleophilic moiety, wherein the ratio of the amount of the reactiveleuco compound present in the leuco composition to the amount of acolored form of the reactive leuco compound present in the leucocomposition is about 4:1 or more, wherein the leuco moiety is selectedfrom the group consisting of diarylmethane leuco moieties, oxazinemoieties, thiazine moieties, hydroquinone moieties, and arylaminophenolmoieties, and wherein the reactive moiety is selected from the groupconsisting of sulfooxyethylsulfonyl moieties, halotriazinyl moieties,quaternary ammoniumtriazinyl moieties, halopyrimidinyl moieties,halopyridazinyl moieties, haloquinoxalinyl moieties, halophthalazinylmoieties, bromoacrylamidyl moieties, and benzothiazolyl moieties.
 2. Theleuco composition of claim 1, wherein the leuco moiety is a univalent orpolyvalent moiety derived by removal of one or more hydrogen atoms froma structure of Formula (II), (III), (IV), or (V)

wherein the ratio of Formula II-V to its oxidized form is about 4:1 ormore; wherein e and f are independently integers from 0 to 4; whereineach R²⁰ and R²¹ is independently selected from the group consisting ofa halogen, a nitro group, alkyl groups, substituted alkyl groups,—NC(O)OR¹, —NC(O)SR¹, —OR¹, and —NR¹R²; wherein each R²⁵ isindependently selected from the group consisting of a monosaccharidemoiety, a disaccharide moiety, an oligosaccharide moiety, apolysaccharide moiety, —C(O)R¹, —C(O)OR¹, —C(O)NR¹R²; wherein each R²²and R²³ is independently selected from the group consisting of hydrogen,an alkyl group, and substituted alkyl groups; wherein R³⁰ is positionedortho or para to the bridging amine moiety and is selected from thegroup consisting of —OR³⁸ and —NR³⁶R³⁷, wherein each R³⁶ and R³⁷ isindependently selected from the group consisting of hydrogen, an alkylgroup, a substituted alkyl group, an aryl group, a substituted arylgroup, an acyl group, R⁴, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; wherein R³⁸is selected from the group consisting of hydrogen, an acyl group,—C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; wherein g and h are independentlyintegers from 0 to 4; wherein each R³¹ and R³² is independently selectedfrom the group consisting of an alkyl group, a substituted alkyl group,an aryl group, a substituted aryl group, an alkaryl, substitutedalkaryl, —C(O)R¹, —C(O)OR¹, —C(O)O³¹ , —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹,—OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R²,—NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹,—P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂; wherein —NR³⁴R³⁵ ispositioned ortho or para to the bridging amine moiety and R³⁴ and R³⁵are independently selected from the group consisting of hydrogen, analkyl, a substituted alkyl, an aryl, a substituted aryl, an alkaryl, asubstituted alkaryl, and R⁴; wherein R³³ is independently selected fromthe group consisting of hydrogen, —S(O)₂R¹, —C(O)N(H)R¹; —C(O)OR¹; and—C(O)R¹; wherein when g is 2 to 4, any two adjacent R³¹ groups maycombine to form a fused ring of five or more members wherein no morethan two of the atoms in the fused ring may be nitrogen atoms; whereinX⁴⁰ is selected from the group consisting of an oxygen atom, a sulfuratom, and NR⁴⁵; wherein R⁴⁵ is independently selected from the groupconsisting of hydrogen, deuterium, an alkyl, a substituted alkyl, anaryl, a substituted aryl, an alkaryl, a substituted alkaryl, —S(O)₂OH,—S(O)₂O⁻, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; wherein R⁴⁰ and R⁴¹ areindependently selected from the group consisting of —OR¹ and —NR¹R²;wherein j and k are independently integers from 0 to 3; wherein R⁴² andR⁴³ are independently selected from the group consisting of an alkyl, asubstituted alkyl, an aryl, a substituted aryl, an alkaryl, asubstituted alkaryl, —S(O)₂R¹, —C(O)NR¹R², —NC(O)OR¹, —NC(O)SR¹,—C(O)OR¹, —C(O)R¹, —OR¹, —NR¹R²; wherein R⁴⁴ is —C(O)R¹, —C(O)NR¹R², and—C(O)OR¹; wherein R¹, R² and R³ are independently selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, and R⁴; R⁴ is a organicgroup composed of one or more organic monomers with said monomermolecular weights ranging from 28 to 500; wherein any charge present inany of the moieties is balanced with a suitable independently selectedinternal or external counterion.
 3. The leuco composition of claim 2,wherein R⁴ is selected from the group consisting of alkyleneoxy,oxoalkyleneoxy, oxoalkyleneamine, epichlorohydrin, quaternizedepichlorohydrin, alkyleneamine, hydroxyalkylene, acyloxyalkylene,carboxyalkylene, carboalkoxyalkylene, and sugar.
 4. The leucocomposition of claim 2, wherein the suitable independently selectedexternal counterions are selected from the group consisting of Na, K,Mg, Ca, iminium, ammonium, phosphonium, fluoride, chloride, bromide,iodide, perchlorate, hydrogen sulfate, sulfate, aminosulfate, nitrate,dihydrogen phosphate, hydrogen phosphate, phosphate, bicarbonate,carbonate, methosulfate, ethosulfate, cyanate, thiocyanate,tetrachiorozincate, borate, tetrafluoroborate, acetate, chloroacetate,cyanoacetate, hydroxyacetate, aminoacetate, methylaminoacetate, di- andtri-chloroacetate, 2-chloro-propionate, 2-hydroxypropionate, glycolate,thioglycolate, thioacetate, phenoxyacetate, trimethylacetate, valerate,palmitate, acrylate, oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzenesulfonate, toluenesulfonate, biphenyl-sulfonate andchlorotoluenesulfonate.
 5. The leuco composition of claim 1, whereinreactive leuco compound comprises at least two reactive moietiescovalently bound to the leuco moiety.